Triphenylmethane dye and process of making same.



ALFRED conzsrrr. or BASEL, SWITZERLAND, Ass'reXoR TO ANILINE COLOUR AND.EXTRACT WORKS, FORMERLY JOHN R. GEIGY, or BASEL, SWITZERLAND..-

rRIPnEnYmmtrn NE-fiYE ANDPRocnss or MAKING SAME.

gatenteol Jan. 21, 1908 Application filed August 1, 1907. Serial No-386.623.

. adapted to be afterwards treated with bichromate, by condensingorthosulfo-benzaldehyde and its derivatives of the general formula (xand y representing hydrogen atoms which can be re laced by halogen, thenitro, sulfoor methy group) for instancei orthosulfo-benz aldehyde CHO:SO H 1 :2) chiorothosulfo-benzaldehyde (CHO :SO H 2G1: 1:2 :4 and122:5) nitroijrthosulfo-benzaldehyde ono zSO HzNO, 112:4. and 1 :5)disulfobenzaldehyde I I cnoso nzs n 12 and 11215disulfomethyl-benzaldehyde (CHO :S( H:CH 1 :2 :4 :5)

and the like with aromatic oxycarbonic acids such as orthocresotinicacid or salicylic acid and by oxidizing the thus producedleuco compoundsin presence, of concentrated sulfuric acid by means of bodies containingnitro genoxids, such as nitrous acid, nitric acid or aromaticnitrocompounds.

In carrying out my process I can proceed in two diiierent ways: Either asolutionof orthosulfo-benzaldehyde in diluted sulfuricacid of percent.is boiled with the arcmatic oxycarbonic acid, and then the leucocompound thus formed is se arated in dry form and transformed intotiedyestufi by a subsequent oxidation by means of a solution of nitrousor nitric acid or an aromatic nitro compound in concentrated sulfuricacid or what has been proved to be more advantageous inmost cases toaccomplish the condensation and oxidation, in the same solution ofconcentrated sulfuric acid isolating the leuco com ound.

p T he following examp es will serve to further illustrite manner inwhich the new coloring matters can be obtained in practice,

without:

but my invention is not limited to these examples.

Exam is I: '21 kilos-of the sodium salt of ortho-su fobenzaldehyde aredissolved in 150 kilos of sulfuric acid of 50 per cent. and boiled with31 kilos of orthocresotinic acid for twelve hours, using a reflux;cooler, at a temperature of 120-125' C. The leuco body will then have searated as amass of small knobs tinted red sh and is filtered ofl,purified by dissolving in water and precipitated with common salt. apowder slightly reddish, easily The leuco compound will behave towardsoxidizing agents as follows. Peroxid of, lead and chloranil show neitherin acid nor in alcoholic solution, anycolor reaction, whereasbichromateof potassium in acid solution- Will react quite singularly: The'solution'will turn slowly red in the cold and uickly red, when heated,then violet and lastly blue, evidently meanwhile forming a lake. I

For oxidation on a large scale nitrosylsulfuric acid may be adopted withadvantage,-

When dried, it is soluble inv water, alcohol and glacial aceticacid',but almost insoluble in benzene and chloroform.

the method being as follows:' 7 kilosofgnitrite of sodium are added bydegreesandwhile stirring to 150 kilos'of concentrated sulfuric acid.After all is well, dissolved, the warin solution is cooled down to 20 C.and 471.3 kilos of the leuco compound are slowly added while the last-mentioned temperature is maintained. The melt soon. turns red and theoxidation is finished within twenty-four hours. This product isintroduced into 150 liters of water, when the coloring matter willseparate tinted a bright red; it is then filtered off, dissolved inwater and precipitated again 1 by means of common salt. en dried itpresents a red powder, easily soluble in water u-ith'an orange-red andin diluted caustic soda lye with a violet color, which whenacidulated,again turns into an orange-red; T he solution is concentrated sulfuricacid is likewise orange-red and diluted with a little water willseparate thecoioring matter in red flakes which however, will againdissolve if dilution is continued on a liberal'scale. Am-

' moni'a will deep n theforange-red aqueous solution into'abrownish-red.

'The dyestufi'dyes wool in an acidulated bath a bright red and'aftertreated with-ibichromate of potassium a brilliantQand-p'ureviolet-blue. The-same violet blue shades are roduc'ed'by dyeing chromemordanted wool.

he new dyestufican also be used for print in- "611 cotton whenmixed-witha chrome fit ;$a t. The chrome dyein' s' excel in very good fastnessj tomilling aswe l as in a fastness to 'gh't hi'therto'unknown with colorsof'the tri'-. phenylmethaneseries.

. I Example II. 296 liters of a solution of 2:4;disulfobenzaldehyde of 9'per' cent. are

.evaporated to dryness and the remaining dry mass dissolved in 140 kilosof concentrated sulfuricflacid. A solution of 20.3 kilos of 111-nitrohenzene-sulfonic acid in 40 kilos of sul- I acirlKas it is;directly obtained by the 'sul'furiz ation of 12 .3 kilos of nitrobenzenewith 48 kilos .offuming sulfuric acid containing twenty-four per cent.of anhydrid) and'27.6 pf-kilos of salicylic acid are then added and thewhole while stirring heated from 90 to 100 0. After 12 to15 hours theformation of the ing. matters of the triphenylrnethane series 'bycondensing the hereinbefore defined orthoc0loring matter is finished.The meltis fpouredinto water, saturated With'lime, the solution filteredand evaporated to dryness.

The resulting calcium salt of the dyest'ufi. forms a dark'violet powder,very soluble in Water with a bluish red color turning into orange whenacidulated and intored violet by addition of caustic soda lye. I35

I It .dyes wool from" an-acid bath in yellowish red shades which by aftertreatment Witha chromate change into a-viole t.

' I Having .;now described my invention What 1. The process for theproduction of colorsulfo-benz'aldehydes in presence of sulfuricacid'with aromatic orthooXy-carboni'c acids and by subsequentlyoxidizing the thus produced leuco, compounds by means ofa solu' tion ofsodium .nitrite in concentrated sul furi'c acid.

2. The process for the production of coloring 'matters of thetriphenylmethane series by condensing the hereinbefore definedorthosulfo-benz aldefhydes --inpresence of concentrated sulfuric acidwith orthocresotinic acid; and by subsequently oxidizing thethus'produced leucocompounds in the same solution of sulfuric'acid byacid.

ing matters of the .triphenylmethaneseries bycondensing the hereinbefore"defined or-' 3. The process .for the production of colore means ofnitrosyl sulfuric thosulfo-benzaldehydes in presence of concentratedsulfuric acid with ortho-cresotinic acid .and by oxidizing thethus'produced leuco compounds by. means of a solution of a bodycontaining an oxid of nitrogen in "sulfuric acid. i A

" 4. As new'articlesof-.manufacture the colorin matters obtainable asdescribed from 3 the 'ereinbefore defined orthosulfo-benz'aldehydes andaromatic. orthooXy-carbonic acids which dyestufis arein the shape oftheir free sulfonioaci-ds from bright red -to' reddishbrown powders,soluble in acidulated water with an orange, in diluted'caustic soda 5lye with a violetc-olor dyeing wool'fromacid bath bright red whichshades by afte'rtreat-- ment with bichromate change into a beauti fu lblue violet,- and yielding the sameblue violet shades chrome salt.

when Printedon cott'Q l h a 5. As new article of manufacture'the'color.- ing matter obtainable as described from the I orthosulfo-b'enzaldehyde and ortho-cresotinio acid, which dyestufi isin theshape of its free sulfonic acid -a brig '0 red powder. soluble inacidulated water \vith an orange, in diluted caustic soda lye 1 th aviolet color, dyeing wool from acid badh-bright red whichshades by;aftertreatment with bichromate change into'a beautiful blue-violet, andyielding the same blue iolet shades when printed on cot-

